Process for production of olefines by dimerization,co-dimerization,polymerization and co-polymerization of olefines



United States Patent Int. c1. (50% 3/10 US. Cl. 260683.15 20 ClaimsABSTRACT OF THE DISCLOSURE Monoolefins are oligomerized using a catalystmixture comprising a cyclobutadiene nickel dihalide and a compound suchas ethylaluminum dichloride or diethylberyllium to give a product with ahigh content of betaand gamma-olefins. The use of ethylene and/orpropylene as the feed with tetramethylcyclobutadiene-nickel-dichlorideor tetraphenylcyclobutadiene-nickel-dichloride as a catalyst componentis illustrated.

By the development of cracking processes in the modern petroleumindustry the low-molecular alpha-olefines, such as ethane, propene andbutene, have become easily available raw materials on a large industrialscale.

Besides the direct utilization in the production of highmolecularcompounds in the plastic industry, the refining processes of these rawmaterials to products in the range C -C play an important part inindustrial, organic chemistry.

It is known that beryllium, aluminium, gallium and indium compounds ofthe types BeR AIR;, and InR in which at least one of the ligands, R,represents an organic hydrocarbon residue of hydrogen, are able toconvert lower olefines to dimerized, trimerized and higher products withhigh alpha-olefine content, and that the presence of finely powderedmetallic cobalt, nickel or platinum increases the selectivity of thesystems favouring the formation of more low-molecular (dimerized)products. In particular, finely powdered metallic nickel in the form ofRaney nickel additions or metallic nickel reduced from nickel compoundsby conversion with a certain amount of the organic main group metalcomponent at higher temperature, has been used. In order to prevent themetallic nickel component from being inactivated during an early phaseof the synthesis, processes have been developed in which acetylene orhydrocarbons with acetylene bonds are added during the conversions. Inthe polymerization of ethane with aluminium-trialkyl and metallic nickelas catalyst, the minimum amount of acetylene which is added is reportedto lie in the range 0.21% of the total quantity of converted ethene(German Patent No. 1,001,981).

Drawbacks of the known oligomerization processes of the Ziegler type,besides the additions of the types of organic compounds described aboveare, that these processes use very high catalyst concentrations of themain group metal compound, up to 20% of the reaction mixture. Also, dueto the high temperatures and pressures which are required during thesyntheses, up to 250 C./200 atm. (German Patent No. 964,642, US. PatentNo. 2,695,327), vary inflammable and explosive mixtures are produced.

A characteristic feature of the said processes, in which transitionalmetal additions are used as co-catalyst, is that these exist in finelypowdered metallic form with the formation of a heterogenous phase in thecatalytic mixtures.

3,442,971 Patented May 6, 1969 Surprisingly we have now found thatcyclodienenickel-dihalides, which in combination with metal-organiccompounds of the metals in 2nd and 3rd main group in the periodic tableare not reduced to metallic nickel, and which in mixtures with the maingroup metal compounds mentioned above represented very active catalystsystems for dimerization, co-dimerization, polymerization andco-polymerization of alpha-olefines from the range C -C at such mildconditions as, for example, 20 C./1 atm., under formation ofmono-olefines in the range C -C with high content of betaandgammaolefines.

As the main group metal component there can be used one or morecompounds of the types Be(R),(Y) )b( )3-b, )b( )3-b and )b( )3-b and/01'their adition compounds with electrondonor compounds such as ethers,phosphines etc., in which R=hydrocarbon radical, preferably alkyl and/or hydrogen, Y=acid radical, such as halogen and alkoxy-groups, a=l2 andb=13.

From the literature it is known that organic ligands, preferably suchcontaining one or more carbon/carbon double or triple bonds, can beattached to a transition metal by electronic interactions between thep-electrons of the ligand and the d-electrons of the transition metalsor free d-electron orbitals (1r-bonds). Compounds which contain suchtypes of bonds are termed 1r-organic transition metal compounds. Commonto the types of organic nickel compounds indicated above is that thesecontain 1r-b0nd6d organic ligands. Since other nickel organic compoundscontaining the same type of bond satisfying the necessary stabilityrequirements exist in addition to the above-mentioned types ofvr-organic nickel compounds, active catalyst components will also befound among these compounds.

The advantage of the process according to the invention is that use ismade of a soluble catalyst having such high activity that the reactionscan take place at substantially lower temperature, pressure and catalystconcentration than those described as favourable in formerly knownoligomerization processes of the Ziegler type. Besides, the compositionof the reaction products differs at essential points from the abovementioned types of processes by the fact that there are formed dimerizedand trimerized mono-olefines with very high content of betaandgamma-olefines. The formation of the active catalyst system is verysimple. It occurs automatically at the mixing of the two types ofcatalyst components, advantageously in the form of solutions in an inertorganic solvent, such as benzene, xylene, heptane or higher parafins, inargon or nitrogen atmosphere. The concentration of the main group metalcompound, as well as the rela tive proportion of the two types ofcompound, can be varied within wide limits. It has been found favourableto the process to use main group metal concentrations within the range0.001-0.100 mole/liter, and a nickelmain group metal molar ratio in therange 1:1-0.01:1.

The process according to the invention can be performed at pressuresfrom fractions of an atmosphere up to very large pressures, limited onlyby the apparatus construction. It is, however, advantageous, out ofregard for temperature control, that the reactions take place atpressures not exceeding atm. The reducing effect which lies in the maingroup metal-carbon bonds BeC, AlC, Ga-C and In-C may lead to a reductionof the nickel compounds, if the temperature during the conversion is toohigh. The reaction temperature should therefore be kept below thetemperature range in which a substantial part of the nickel compound inthe course of the conversion is destroyed by reduction to preferably notexceeding 100 C. The highest reaction temperatures can be selected inthe processes which make metallic nickel,.

use of the most stable cyclobutadiene nickel compounds in combinationwith the least reduction-active main group metal compounds as catalysts.

The process can be carried out either discontinuously, for example, byplacing the catalyst components together with a solvent, if necessary,in a thermostat-regulated reaction vessel, passing the monomer or themonomer mixture for some time, e.g. 1-5 hours, into the catalystmixture, and then extracting the reaction product by the usual workingmethods, or continuously, for example by passing the monomer or themonomer mixture through the catalyst mixture, with subsequent continuousisolation of the reaction product from the outflowing gas mixture.Unreacted monomer and solvent, if any, and catalyst are separated fromthe reaction product during the isolation of the latter and are suitablyrecirculated to the reaction vessel. By the process according to theinvention, in which the monomer is a liquid, solvent can be omitted withadvantage. In addition to the alpha-olefines, mixtures of their isomericcompounds may also be used as raw material for the processes, due to theisomerization activity of the catalyst systems.

APPARATUS AND TECHNIQUE For the examples 1-9 the following apparatus andwork technique were used:

One or more of the above-mentioned types of nickel compounds are placedin a thermostat-regulated glass reaction flask, equipped with a magneticstirrer, reflux condenser and dropping funnel with pressure-equalizingmeans. On the top of the reflux condenser there was a possibility ofconnection to vacuum, highly purified nitrogen and highly purifiedstarting-monomer for the syntheses. The apparatus was evacuated for 1hour, then filled with nitrogen. In the course of the nitrogen flushingthe desired quantity of abs. solvent was added to the reaction flask. Amain group metal compound of the above-mentioned type or mixtures ofthese are, if necessary diluted with solvent, then added to the droppingfunnel in a nitrogen atmosphere. The whole apparatus is then carefullyevacuated three times and after each time filled with thestarting-monomer at atmospheric pressure. At reaction time zero the twocatalyst components, each saturated with the starting-monomer, are mixedunder agitation in the reaction flask. The inflow velocity of thestarting-monomer required to maintain constant pressure in the reactionflask (1 atm.) was measured with a capillary flow meter as a function ofreaction time. The bath temperature was kept constant within the limitsi0.05 C. by means of a water-circulation thermostat. After a certainreaction time the conversion was stopped and the reaction mixture wasgas-chromatographically analyzed.

For the Examples -13 the following apparatus and technique were used:

The reactions were carried out in a non-magnetic, acidresistant steelautoclave having a volume of 200 ml. The autoclave was connected with aglass container which could be evacuated. The connection between the twovessels could be closed by means of a high pressure valve. Before theexperiment the autoclave and glass container were evacuated to less than0.5 mm. Hg in 30 min. The valve between the two vessels was closed andthe glass container filled with highly purified nitrogen. The catalystcomponents and the solvent were then poured into the glass container ina nitrogen atmosphere.

By opening the valve between the two vessels the catalyst solution wassucked into the evacuated autoclave. The connection to the vacuum pumpwas out 01f in advance. The autoclave was then filled with monomer tothe indicated pressure, which was kept constant during the wholereaction period. The autoclave was fitted with a magnetic stirrer andplaced in a water bath with the stated temperatures i0.1 C. The reactionmixtures were gaschromatographically analyzed.

EXAMPLE 1 Temperature: 28 C. Pressure: 1 atm. Solvent: 44 g. benzene.Catalyst: 35.7 mg. tetramethylcyclobutadienenickel-dichloride, 127 mg.aluminium-monoethyl-dichloride. Monomer: ethene, Reaction time: 60 min.Reaction product formed: 15 g. Composition of product: 78% C -olefines(of which 1.3% butene-l, 72.6% butene 2-trans and 26.1% butene-2-cis).

17% C -olefines (of which 20% heXene-3-cis and trans, 55%hexene-Z-trans, 14% hexene-2-cis and 11% 3-methyl-pentene-2-cis andtrans). 5% higher than C olefines.

EXAMPLE 2 Temperature: 20 C. Pressure: 1 atm. Solvent: 44 g. benzene.Catalyst: 119 mg. tetramethylcyclobutadienenickel-dichloride, 127 mg.aluminium-monoethyl-dichloride. Monomer: propene. Reaction time: 60 min.Reaction product formed: 20 g.

Composition of product: C -olefines (of which 0.9% 4-methylpentene-1,2.8% 4-methylpentene-2-cis, 23.1% 4-methyl-pentene-2-trans, 3.6%Z-methylpentene-l, 42.5% 2-methyl-pentene-2, 4.4% hexene-3-cis andtrans, 13.6% hexene-Z-trans, 4.7% hexene-2-cis and 4.4% 2,3-dimethylbutene-Z). 5% higher than C -olefines.

EXAMPLE 3 Temperature: 20 C. Pressure: 1 atm. Solvent: 44 g. benzene.Catalyst: 35.7 mg. tetramethylcyclobutadienenickel-dichloride, 127 mg.aluminium-monoethyl-dichloride. Monomer: ethene/propene=% (gas volume at20 C./1 atm.). Reaction time: 30 min. Reaction product formed: 9 g.

Composition of product: 2% C -olefines (of which, 72.7% butene-2-trans,27.3% butene-2-cis). 28% C -olefines (of which, 1.0% Z-methyIbutene-l,5.5% 2-methylbutene-2, 72.4% pentene-Z-trans, 21.1% pentene-Z-cis). 65%C -olefines (of which, 1.5% 4-methylpentene-1, 7.3%4-methylpentene-2-cis, 52.4% 4-methylpentene-2- trans, 4.8% heXene-3-cisand trans, 17.5% hexene-2-trans, 12.7% 2-methylpentene-2 and 3.8%hexene-Z-cis). 5% C -olefines.

EXAMPLE 4 Temperature: 20 C. Pressure: 1 atm. Solvent: 37 g. benzene.Catalyst: 30 mg. tetramethylcyclobutadienenickel-dichloride, 180 mg.aluminium monoethyl dibromide. Monomer: ethene. Reaction time: 60 min.Reaction product formed: 2.3 g. Composition of product: 80% C -olefines(of which approx. butene-2-trans). 15% C olefines (of which 31%hexene-3-trans, 69% hexene- 2-trans). 5% higher than C -olefines.

EXAMPLE 5 Temperature: 20 C. Pressure: 1 atm. Solvent: 40 g. benzene.Catalyst: 30 mg. tetramethylcyclobutadienenickel-dichloride, mg.dialuminium-triethyl-monoethoxy-dichloride. Monomer: ethene. Reactiontime: min. Reaction product formed: 7.5 g.

Composition of product: 82.1% C -olefines (of which 1.8% butene-l, 70.0%butene-Z-trans, 28.2% butene-Z- cis). 14.9% C -olefines (of which 6.7%hexene-3-cis and trans, 3.1% 2-ethylbutene-1, 18.3% hexene-Z-trans,20.1% 3-methylpentene-2-trans, 6.7% hexene-2-cis and 45.1% 3-methylpentene-Z-cis). 3% higher than C -oleflnes.

EXAMPLE 6 Temperature: 20 C. Pressure: 1 atm. Solvent: 44 g. benzene.Catalyst: 35.7 mg. tetramethylcyclobutadienenickel-dichloride, 217 mg.aluminium-diphenyl-monochloride +131.2 mg. triphenylphosphine. Monomer:ethene. Reaction time: min. Reaction product formed 4.5 g.

Composition of product: 97% C -olefines (of which 9.2% butene-l, 62.5%butene-Z-trans, 28.3% butane-2- cis). 3% higher than C -olefines,

Temperature: 20 C. Pressure: 1 atm. Solvent: 44 g. benzene. Catalyst:119.0 mg. tetramethylcyclobutadienenickel-dichloride +l31.2 mg.triphenylphosphine, 34 mg. berylliumdiethyl (added in this order).Monomer: ethene. Reaction time: 30 min. Reaction product formed: g.

Composition of product: 91% C -olefines (of which 2.4% butene-l, 69%butene-Z-trans, 28.6% butene-Z-cis), 8% C -olefines (of which 29.2%hexene-3-+ 2-ethylbutene-l, 20.2% hexene-2-trans, 18.0%3-methylpentene-2- trans, 32.6% 3-methylpentene-2-cis). 1% higher than Colefines.

EXAMPLE 8 Temperature: 20 C. Pressure: 1 atm. Solvent: 44 g. benzene.Catalyst: 75 mg.tetramethylcyclobutadiene-triphenylphosphine-nickel-dichloride, 127 mg.aluminiummonoethyl-dichloride. Monomer: ethene. Reaction time: 30 min.Reaction product formed: 4 g.

Composition of product: 46.6% C -olefines (of which 2% butene-l, 69.5%butene-2-trans and 28.5% :butene-Z- cis), 48.4% C -olefines (of which4.0% hexene-3-cis and trans, 7.0% 2-ethylbutene-1, 9.0% hexene-Z-trans,26.0% 3-methylpentene-2-trans, 4.0% hexene-Z-cis, 50%3-methyl-pentene-Z-cis). 5% higher than C -olefiines.

EXAMPLE 9 Temperature: 20 C. Pressure: 1 atm. Solvent: 44 g. benzene.Catalyst: 43.8 mg. tetraphenylcyclobutadienenickel-dichloride, 127 mg.aluminium-monoethyl-dichloride. Monomer: ethene. Reaction time: 30 min.Reaction product formed: 5 g.

Composition of product: 72% C -olefines (of which 7.5% butene-l, 67.3%butene-Z-trans, 25.2% butene-2- cis), 26% C -olefines (of which 12.2%hexene-3-cis and trans, 25.1% hexene-2-trans, 15.5% 3-methylpentene-2-trans, 7.4% hexene-Z-cis, 39.8% 3-methylpentene-2-cis). 2% higher than C-olefines.

EXAMPLE 10 Temperature: 25 C. Pressure: 5 atm. Solvent: 44 g. benzene.Catalyst: 29.8 mg. tetramethylcyclobutadienenickel-dichloride, 190 mg.aluminium-monoethyl-dichloride +1965 mg. triphenylphosphine. Monomer:propene. Reaction time: 60 min. Reaction product formed: 35 g.

Composition of product: 92% C -olefines (of which 1.5%4-methylpentene-1, 4.8% 4 methylpentene 2 cis, 23.0%4-methyl-pentene-2-trans, 9.31% Z-methyIpentene-l and hexene-l, 4.7%hexene-3-cis and trans, 13.1% hexene- 2-trans, 37.1% 2-methyl-pentene-2,3.9% hexene-Z-cis and 2.6% 2,3-dimethylbutene-2). 8% higher than Colefines.

EXAMPLE 11 Temperature: 0 C. Pressure: 41 atm. Solvent: 44 g. benzene.Catalyst: 35.7 mg. tetramethylcyclobutadienenickel-dichloride, 127 mg.aluminium-monoethyl-dichloride. Monomer: ethene. Reaction time: 60 min.Reaction product formed: 70 g.

Composition of product: 60% C -olefines (of which 7.0% butene-l, 65.5%butene-Z-trans, 27.5% butene-Z- cis), 30% C -olefines (of which 1.53-methylpentene-1,

0.7% hexene-l, 12.0% hexene-3-cis and trans, 10.6% 2- ethylbutene-l,22.0% heXene-2-trans, 13.6% 3-methylpentene-Z-trans, 8.0% hexene-Z-cis,31.6% 3-methylpentene- 2-cis). 10% higher than C -olefines.

EXAMPLE 13 Temperature: C. Pressure: 5 atm. Solvent: 44 g. benzene.Catalyst: 59.5 mg. tetramethylcyclobutadienenickel-dichloride, 254 mg.aluminium-monoethyl-dichloride. Monomer: propene. Reaction time: 60 min.Reaction product formed: 7 g.

Composition of product: 63% C -olefines (of which 0.8% 4 methylpentene1, 4.2% 4-methylpentene-2-cis, 24.1% methylpentene-Z-trans, 0.5%Z-methyl-pentene-l and hexene-l, 8.8% hexene-3-cis and trans, 24.6%hexene-Z-trans, 25.3% Z-methylpentene-Z, 6.7% hexene-Z-cis, 5.0%2.3-dimethylbutene-2). 27% higher than C -olefines.

I claim:

1. In a process for the production of monoolefines in the range of C -Cby the catalytic conversion of olefines in the range of C -C theimprovement according to which the catalyst is a catalytic mixture ofone or more cyclobutadiene nickel diahalides and one or more compoundsselected from the group consisting of and Me(R) (Y) in which R isselected from the group consisting of hydrocarbon radicals and hydrogen,Y is an acid radical, a is a number from 1 to 2, b is a number from 1 to3, and Me is selected from the group consisting of Al, Ga and In.

2. The improvement according to claim 1 wherein the cyclobutadienenickel dihalides are employed as addition compounds with electron-donorcomponents.

3. The improvement according to claim 1, wherein the compounds selectedfrom the group consisting of and Me(R),,(Y) are employed as additioncompounds with electron-donor components.

4. The improvement according to claim 1, wherein both the cyclobutadienenickel dihalides and the compounds selected from the group consisting ofand Me(R) (Y) are employed as addition compounds with electron-donorcomponents.

5. In a process for the production of monoolefines in the range of C -Cby the catalytic conversion of olefins in the range of C -C theimprovement according to which the catalyst is a catalytic mixture ofone or more cyclobutadiene nickel dihalides and one or more compoundsselected from the group consisting of Be(R) (Y) and Me(R) (Y) in which Ris selected from the group consisting of alkyl and aryl, Y is selectedfrom the group consisting of halogen and alkoxy, a is a number from 1 to2, b is a number from 1 to 3, and Me is selected from the groupconsisting of Al, Ga and In.

6. The improvement according to claim 5, wherein the cyclobutadienenickel dihalides are used as addition compounds with electron-donorcomponents.

7. The improvement according to claim 5, wherein the compounds selectedfrom the group consisting of )a( )2-a and Me(R) (Y) are employed .asaddition compounds with electron-donor components.

8. The improvement according to claim 5 wherein the cyclobutadienenickel dihalides and the compounds selected from the group consisting ofBe(R) (Y) and are used as addition compounds with electron-donorcomponents.

9. In a process for the production of monoolefines in the range of C -Cby the catalytic conversion of olefins in the range of C -C theimprovement according to which the catalyst is a catalytic mixture ofone or more cyclobutadiene-nickel-dihalides and one or morealuminumalkylhalides.

10. The improvement according to claim 9 wherein thecyclobutadiene-nickel-dihalides are used as addition compounds withelectron-donor components.

11. The improvement according to claim 9 wherein thealuminium-alkylhalides are used as addition compounds withelectron-donor components.

12. The process according to claim 9 wherein thecyclobutadiene-nickel-dihalides and the aluminium-alkylhalides are usedas addition compounds with electron-donor components.

13. In a process for the production of monoolefines in the range of C -Cby the catalytic conversion of ethene and propene at a temperature of upto 100 C. and at a pressure of up to 100 atmospheres, the improvementaccording to which the catalyst is a catalytic mixture ofcyclobutadiene-nickel-dihalides, and an aluminium-alkylhalide.

14. The improvement according to claim 13 wherein thecyclobutadiene-nickel-dihalides are used as addition compounds withtriphenyl phosphine.

15. The improvement according to claim 13 wherein thealuminium-alkylhalide is used as an addition compound with triphenylphosphine.

16. The improvement according to claim 13 wherein thecyclobutadiene-nickel-dihalides and the aluminiumalkylhalide are used asaddition compounds with triphenyl phosphine.

17. In a process for the production of mono-olefines in the range of C Cby the catalytic conversion of ethene and propene at a temperature of upto 100 C. and at a pressure of up to 100 atmosphere, the improvementaccording to which the catalyst is a catalytic mixture of acyclobutadiene nickel-compound selected from the group consisting oftetramethylcyclobutadiene-nickeldichloride, andtetraphenylcyclobutadiene-nickeldichloride, and a main group metalcompound selected from the group consisting ofaluminium-monoethyl-dichloride, aluminiummonoethyl-dibromide,aluminium-diphenyl-monochloride, dialuminium triethylmonoethoxydichloride and beryliumdiethyl.

18. The'improvement according to claim 17, wherein the'cyclobutadienenickel compound is used as an addition compound with triphenylphosphine.

19. The improvement according to claim 17 wherein the main group metalcompound is used as an addition compound with triphenyl phosphine.

20. The improvement according to claim 17 wherein the cyclobutadienenickel compound and the main group metal compound are used as additioncompounds with triphenyl phosphine.

References Cited UNITED STATES PATENTS 3,134,824 5/1964 Walker et al260683.15 3,379,706 4/1968 Wilke 260683.15 X 2,969,408 1/1961 Nowlin etal. 3,321,546 5/1967 Roest et al.

FOREIGN PATENTS 651,596 2/1965 Belgium.

PAUL M. COUGHLAN, JR., Primary Examiner.

U.S. C1. X.R. 252431

